CN101440137A - Preparation of monodisperse porous organic polymer microsphere supported metallocene catalyst - Google Patents
Preparation of monodisperse porous organic polymer microsphere supported metallocene catalyst Download PDFInfo
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- CN101440137A CN101440137A CNA2008100516325A CN200810051632A CN101440137A CN 101440137 A CN101440137 A CN 101440137A CN A2008100516325 A CNA2008100516325 A CN A2008100516325A CN 200810051632 A CN200810051632 A CN 200810051632A CN 101440137 A CN101440137 A CN 101440137A
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- 239000004005 microsphere Substances 0.000 title claims abstract description 57
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 43
- 239000012968 metallocene catalyst Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 150000001336 alkenes Chemical class 0.000 claims abstract description 5
- 238000011068 loading method Methods 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 54
- 239000000839 emulsion Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 206010042674 Swelling Diseases 0.000 claims description 26
- 230000008961 swelling Effects 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 239000004793 Polystyrene Substances 0.000 claims description 17
- 229920002223 polystyrene Polymers 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000003381 stabilizer Substances 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 7
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 claims description 5
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000012442 inert solvent Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphenyl group Chemical group C1=CC=CC2=CC3=CC=C4C=C5C=CC=CC5=CC4=C3C=C12 JQQSUOJIMKJQHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 13
- 125000000524 functional group Chemical group 0.000 abstract description 6
- 239000004698 Polyethylene Substances 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 4
- -1 polyethylene Polymers 0.000 abstract description 4
- 229920000573 polyethylene Polymers 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000005977 Ethylene Substances 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910007926 ZrCl Inorganic materials 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 101150019148 Slc7a3 gene Proteins 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 101100492805 Caenorhabditis elegans atm-1 gene Proteins 0.000 description 1
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000006250 specific catalysis Methods 0.000 description 1
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a method for preparing a monodisperse porous organic polymer microsphere carrier metallocene catalyst, which comprises: preparing a monodisperse porous organic polymer microsphere carrier A, loading a metallocene catalyst B onto the carrier A to obtain a carrier primary metallocene catalyst which forms a target catalyst together with a cocatalyst C. In comparison with an inorganic carrier rigid surface of an inorganic carrier, an organic polymer carrier and a final polymer are more 'affiliated' and the synthesized polymer by the catalyst has low content of inorganic ash; a porous structure of the catalyst has bigger specific surface, contributes to the release of a load and an active center of the catalyst, and more contributes to gradually breaking of carriers in catalyzing olefin polymerization; compared with functional carriers of the microsphere polymer, the carrier structure which is added with functional group monomer for polymerization during synthesis is definite and the functional groups are evenly distributed in the carriers. The polyethylene obtained through catalysis of the catalyst is powdered in a macroscopic view and is strip-shaped with flakes congregating in a microscopic view.
Description
Technical field
The present invention relates to monodisperse porous organic polymer microsphere supported metallocene Preparation of catalysts method.
Background technology
Advantages such as polyolefine has the cost performance height, mechanical property is good and thermal characteristics is stable are widely used in every field such as industrial or agricultural, health care and daily life, are the macromolecular materials that has a large capacity and a wide range most.Catalyzer is polyolefinic core, and metallocene catalyst causes people's extensive attention because of its copolymerization performance that catalyzed polymerization alkene activity is high, the active centre is single, excellent, to the effective control of polymer architecture.Up to the present more than 10,000 piece of research paper delivered in the metallocene catalyst field according to incompletely statistics, applied for more than 4,000 part of patent.According to the processing requirement of present gas phase or slurry polymerization, catalyzer need carry out loadization, and purpose is in order to prevent catalyzer bimolecular inactivation, to make polymerization process steadily and improve the apparent density of polymkeric substance.Present stage is mainly adopted SiO
2, MgCl
2, Al
2O
3In the carrier of inorganics, because the strong electrostatic interaction between these carriers and the metallocene makes that the catalytic performance of metallocene catalyst changes on the one hand as catalyzer; The residual organic/inorganic substance of these inorganic carrier catalyst gained polyolefine on the other hand; The more important thing is that these hard carrier particle fragments will bring polymer morphology and the purity of not expecting.By contrast, the organic polymer supported metallocene catalyst provide one with the similar chemical environment of homogeneous catalyst.With respect to inorganic carrier inflexible surface, organic carrier seems then that with final polymkeric substance " avidity " is more arranged.And organic carrier preparation is easier, cost is lower, easier carry out functionalized to satisfy specific catalysis requirement.The inorganic impurity of the catalytic polyolefine remnants of organic carrier metallocene catalyst is few, and the easier control of polymer morphology can satisfy the requirement in the high field such as the needs insulativity that looks like cable sheathing, so the organic polymer carrier has progressed into people's sight.
The preparation method of organic polymer supported catalysts comprises at present: 1, it is functionalized that organic high polymer microsphere (typical as polystyrene microsphere) is carried out the back, it is functionalized as Chinese patent CN1624005 linear polystyrene to be carried out chloromethyl, is undertaken crosslinked by the D-A reaction.The shortcoming that this method mainly exists is that the structure of functional groups of carrier is indeterminate, the skewness of functional group in carrier; 2, metallocene catalyst and vinylbenzene with olefin functionalities carry out copolymerization, as the synthetic a kind of P (S-co-(R1) of Chinese patent CN1257875A
m(R2)
nM) from the metallocene catalyst of loading type high molecular.3, in carrier synthetic, introduce the functional monomer and carry out copolymerization, be polymer carrier as the crosslinked polystyrene copolymerization vinylcarbinol of Chinese patent CN1396186 employing.What reported at present is solid-core support only, and this solid-core support is unfavorable for the load of catalyzer on the one hand, and solid-core support is unfavorable for that carrier is broken in the catalyzed ethylene polymerization process on the other hand, is unfavorable for that the active centre discharges.
Summary of the invention
The invention provides monodisperse porous organic polymer microsphere supported metallocene Preparation of catalysts method.
The present invention prepares monodisperse porous organic polymer microsphere supported A by two step seed swelling methods, metallocene catalyst B loaded to obtain the supported metallocene Primary Catalysts on the carrier A, constitute the monodisperse porous organic polymer microsphere supported metallocene catalyzer with promotor C.This supported catalysts provides a better and similar chemical environment of homogeneous catalyst, and with respect to inorganic carrier inflexible surface, this organic polymer carrier seems then that with final polymkeric substance " avidity " is more arranged, and synthetic polyolefine inorganic ash content is low; With respect to existing solid organic carrier, because its vesicular structure has bigger specific surface area, help the load of catalyzer and the release in active centre, it is progressively broken in the catalysis in olefine polymerization process that this vesicular structure more helps carrier; With respect to functionalized carrier behind the polymer microsphere, this carrier structure that adds monomer's copolymerization when synthetic is clear and definite, and functional group is evenly distributed in carrier.
Monodisperse porous organic polymer microsphere supported metallocene Preparation of catalysts method provided by the invention is as follows:
The composition of catalyzer: catalyzer is made up of A, B and C; Described A is a monodisperse porous organic polymer microsphere, and it is polystyrene, Vinylstyrene and vinyl cyanide thing, is abbreviated as P (St-co-DVB-co-AN);
Described B is a metallocene, and its molecular formula is Cp
xMCl
y, in the formula, x=1 or 2, y=2 or 3, Cp are cyclopentadienyl group and derivative thereof, M is Ti or Zr;
Described C is a promotor, and it is methylaluminoxane MAO, modified methylaluminoxane MMAO or three penta phenyl fluoride boron B (C
6F
5)
3
Preparation of catalysts:
1) preparation of monodisperse porous organic polymer microsphere [(P (St-co-DVB-co-AN microballoon]
The preparation of a, linear polystyrene seed microballoon
Mechanical stirring is being housed, reflux condensing tube, nitrogen conduit, adding weight proportion in the four-hole reactor of temperature-detecting device is the vinylbenzene of 10:44:44:0.1:2, ethanol, ethylene glycol monoemethyl ether, Diisopropyl azodicarboxylate and polyvinylpyrrolidone PVP K-30 stir, stirring velocity is 60～120rpm, 60～80 ℃ of polymerization 12～24h of water-bath under the nitrogen protection, after reaction finishes, with reaction solution by centrifugal settling, remove supernatant liquid, to precipitate and use ethanol respectively, water washing, dry in vacuum drying oven, obtain the linear polystyrene seed microballoon of uniform particle diameter;
B, the seed swelling polymerization of two steps prepare monodisperse porous organic polymer microsphere supported A
(1) aqueous ethanolic solution of configuration 0.25wt% sodium laurylsulfonate obtains dispersion liquid; Described ethanol water is solvent, and by the ethanol of mass ratio 5:1: water is formed;
(2) disperse polystyrene seed with dispersion liquid, wherein polystyrene seed: the mass ratio of dispersion liquid is 0.5:10～30, and ultra-sonic dispersion 5～20min obtains seed emulsion;
(3) disperse the 1-chlorododecane to help swelling agent with dispersion liquid, wherein the 1-chlorododecane helps swelling agent: the dispersion liquid mass ratio is 0.5:20～40, and ultra-sonic dispersion 10～60min obtains the bloated agent emulsion of hydrotropy;
(4) scattered seed emulsion and the scattered bloated agent emulsion of hydrotropy are mixed, place and mechanical stirring is housed, reflux condensing tube, nitrogen conduit is in the four-hole reactor of temperature-detecting device, in 25～35 ℃, swelling 8～24h under 80～120rpm carries out the first step swelling, obtains the activated seed emulsion;
(5) with dispersion liquid dispersing and mixing monomer, initiator, pore-creating agent; Wherein, mix monomer, initiator, pore-creating agent, dispersion liquid mass ratio are 10:0.1:10:30～60, and described mix monomer is made up of vinylbenzene, Vinylstyrene and other alkene, and each monomer proportion is not limit; Initiator is a dibenzoyl peroxide; Pore-creating agent is toluene, normal heptane or other inert solvents, and their ratio is not limit; Ultra-sonic dispersion 10～60min obtains mix monomer, initiator and pore-creating agent emulsion; Described other inert solvents comprise organic acid, alcohol, ester, aromatic solvent or have 12 carbon with interior any replacement aliphatic hydrocarbon;
(6) after the first step swelling finishes, scattered mix monomer, initiator and pore-creating agent emulsion are joined in the activated seed emulsion in (4) step, in 25～35 ℃, swelling 8～24h under 80～120rpm carries out the second step swelling, obtains the swollen microsphere emulsion;
(7) the configuration 5wt%PVP K-30 aqueous solution obtains stabiliser solution;
After (8) second step swellings finish; the swollen microsphere emulsion is transferred to standing demix in the separating funnel; remove the not remaining monomer of swollen; swollen microsphere emulsion after separating is transferred in the four-hole reactor; according to stabiliser solution: the mass ratio 2:1 of the swollen microsphere emulsion after the separation adds 5wt%PVP K-30 stabiliser solution; 60～80 ℃ of polymerization 12～24h of water-bath under the nitrogen protection; after reaction finishes with reaction solution centrifugal settling; remove supernatant liquid; to precipitate and use ethanol respectively; water washing; use the methylene dichloride extracting, vacuum-drying obtains monodisperse porous organic polymer microsphere supported A
2) preparation of monodisperse porous organic polymer microsphere supported metallocene
Under the anhydrous and oxygen-free condition,, carrier is carried out load according to a kind of in following three kinds of known typical supported catalyst agent methods with described monodisperse porous organic polymer microsphere supported A;
Direct and the carrier reaction of carrying method 1-metallocene catalyst:
Metallocene catalyst+monodisperse porous organic polymer microsphere supported A → monodisperse porous organic polymer microsphere supported A supported catalyst;
Carrying method 2-metallocene catalyst reacts with MAO earlier, reacts with carrier then:
Metallocene catalyst+MAO →+monodisperse porous organic polymer microsphere supported A → monodisperse porous organic polymer microsphere supported A supported catalyst;
Carrying method 3-monodisperse porous organic polymer microsphere supported A+MAO →+metallocene catalyst → monodisperse porous organic polymer microsphere supported A supported catalyst;
After any one above-mentioned mode of loading finishes, remove solvent, vacuum-drying obtains the monodisperse porous organic polymer microsphere supported metallocene Primary Catalysts; This metallocene Primary Catalysts and promotor C constitute the monodisperse porous organic polymer microsphere supported metallocene catalyzer.
The catalyst ethylene polymerization activity detects and carries out in 0.1L, the 1L autoclave under the anhydrous and oxygen-free condition, parameter according to following table is carried out catalyzed ethylene polymerization, reaction finishes the ethanolic soln termination reaction of back with hydrochloric acid, products therefrom is filtered, with washing with alcohol for several times, vacuum-drying obtains the white powder shaped polyethylene.
| Type of solvent | Toluene, hexane |
| Solvent volume/ml | 60～600 |
| The catalyzer of high molecular/μ molZr | 1～15 |
| Al/Zr | 200～2000 |
| Polymerization temperature/℃ | 25-90 |
| Polymerization pressure/atm | 1～10 |
| Polymerization time/min | 1～120 |
Beneficial effect: supported catalysts of the present invention provides a better and similar chemical environment of homogeneous catalyst, with respect to inorganic carrier inflexible surface, this organic polymer carrier seems then that with final polymkeric substance " avidity " is more arranged, and synthetic polyolefine inorganic ash content is low; With respect to existing solid organic carrier, because its vesicular structure has bigger specific surface area, help the load of catalyzer and the release in active centre, it is progressively broken in the catalysis in olefine polymerization process that this vesicular structure more helps carrier; With respect to functionalized carrier behind the polymer microsphere, this carrier structure that adds monomer's copolymerization when synthetic is clear and definite, and functional group is evenly distributed in carrier.Active and the homogeneous phase Cp of catalyzed ethylene polymerization
2ZrCl
2Catalytic activity is suitable.With 60 ℃ of polymerization temperatures, polymerization pressure 5atm, Al/Zr=1000, catalyzed ethylene polymerization is an example in the 80ml toluene, the carried catalyst activity is 354kgPE/molZr.h.atm, homogeneous Cp
2ZrCl
2Catalytic activity is 371kgPE/molZr.h.atm.Be Powdered on the gained polyethylene macroscopic view, accumulative piece strip in the form of sheets on the microcosmic, electromicroscopic photograph is seen accompanying drawing.
Description of drawings
Fig. 1 is the electromicroscopic photograph of the supported metallocene catalyst carrier that the present invention relates to.
Fig. 2 is a supported metallocene catalyst catalyzed ethylene polymerization gained polyethylene electromicroscopic photograph of the present invention.
Embodiment
Embodiment 1: the preparation of polystyrene seed (PS)
Mechanical stirring is being housed, reflux condensing tube, nitrogen conduit, thermometer the four-hole reactor in to add weight proportion be vinylbenzene, ethanol, ethylene glycol monoemethyl ether, Diisopropyl azodicarboxylate and the PVP K-30 of 10:44:44:0.1:2; Stirring velocity is 80rpm, 70 ℃ of polymerization 24h of water-bath under the nitrogen protection.After reaction finishes with reaction solution by centrifugal settling, remove supernatant liquid, will precipitate and use ethanol, water washing respectively, drying in vacuum drying oven, obtaining particle diameter is the homogeneous PS seed microballoon of 1.5 μ m;
Embodiment 2: the preparation of monodisperse porous polymer microsphere
(1) aqueous ethanolic solution of configuration 0.25wt% sodium laurylsulfonate, described ethanol water is solvent, ethanol: quality obtains dispersion liquid than 5:1;
(2) get the 25g dispersion liquid, add 0.5g polystyrene seed microballoon, ultra-sonic dispersion 5～20min obtains seed emulsion;
(3) get the 25g dispersion liquid, add 0.5g 1-chlorododecane and help swelling agent, ultra-sonic dispersion 10～60min obtains the bloated agent emulsion of hydrotropy;
(4) scattered seed emulsion and the bloated agent emulsion of hydrotropy are mixed, place mechanical stirring is housed, reflux condensing tube, nitrogen conduit, in the four-hole reactor of thermometer, in 30 ℃, swelling 8～24h under the 120rpm; Carry out the first step swelling, obtain the activated seed emulsion;
(5) get the 40g dispersion liquid, add 2g vinylbenzene, 6g Vinylstyrene, 2g vinyl cyanide, 0.1g dibenzoyl peroxide, 10g toluene.Ultra-sonic dispersion 30min obtains mix monomer, initiator, pore-creating agent emulsion;
(6) after the first step swelling finishes, scattered mix monomer, initiator, pore-creating agent emulsion joined carry out the second step swelling, swelling 8～24h under 30 ℃ of 120rpm in the activated seed emulsion; Obtain the swollen microsphere emulsion;
(7) the configuration 5wt%PVP K-30 aqueous solution obtains stabiliser solution;
After (8) second step swellings finish; the swollen microsphere emulsion is transferred to standing demix in the separating funnel; remove the not remaining monomer of swollen; swollen microsphere emulsion after separating is transferred in the four-hole reactor; according to stabiliser solution: the swollen microsphere quality of the emulsion after the separation adds 5wt%PVP K-30 stabiliser solution than 2:1; 60～80 ℃ of polymerization 12～24h of water-bath under the nitrogen protection; after reaction finishes with reaction solution centrifugal settling; remove supernatant liquid; to precipitate and use ethanol respectively; water washing; use the methylene dichloride extracting, vacuum-drying promptly obtains the functionalized monodisperse porous polymer microsphere 3PSDA3 of cyano group of 4.58 μ m.
The synthetic batching of other contrasts PSDA microballoon and final thus obtained microsphere particle diameter, specific surface area see the following form.
Wherein T is a toluene, and H is a normal heptane
Embodiment 3: the load of metallocene catalyst
Under anhydrous and oxygen-free nitrogen protection condition; 1g 3PSD3 polymer microballoon is changed in the Schlenk filtering type reactor; add MMAO according to Al/N=7; 50ml toluene; 50 ℃ of heating in water bath magnetic agitation 12h; reactor is inverted toluene and excessive MMAO in the extractor system, cleans repeatedly 3 times with toluene.Add Cp according to Al/Zr=50
2ZrCl
2, 50ml toluene, 50 ℃ of heating in water bath magnetic agitation 12h are inverted toluene and excessive MMAO in the extractor system with reactor, clean repeatedly 3 times with toluene, at last the toluene in the system are drained, and catalyzer is shifted to put in the prior peace bottle that toasted preserve.The catalyzer Cat3 zirconium content of preparation is 20.44mg/g.
The carrier loaded following table that the results are shown in of PSDA:
| Carrier | Catalyzer | Zirconium import volume/(μ g/mg) | Aluminium import volume/(μ g/mg) |
| 3PSDA?1 | Cat1 | 3.292 | 140.1 |
| 3PSDA?2 | Cat2 | 4.075 | 149.9 |
| 3PSDA?3 | Cat3 | 21.13 | 117.2 |
| 3PSDA?4 | Cat4 | 19.25 | 116.7 |
| 3PSDA?5 | Cat5 | 18.61 | 113 |
Embodiment 4: catalyzed ethylene polymerization
Catalyzed ethylene polymerization carries out in the 0.1L autoclave under the anhydrous and oxygen-free condition, adds toluene 80ml successively in reaction system, contains the catalyzer of the high molecular of 4.7 μ molZr, and Al/Zr=200, ethene pressure 5atm are in 50 ℃ of reaction 30min.With the ethanolic soln termination reaction that contains 1% (weight ratio) hydrochloric acid, products therefrom is filtered, with washing with alcohol for several times, in 50 ℃ of vacuum-drying 24h.Catalytic activity is 117kgPE/molZr.atm.h.
Catalyzed ethylene polymerization carries out in the 0.1L autoclave under the anhydrous and oxygen-free condition, adds toluene 80ml successively in reaction system, contains the catalyzer of the high molecular of 3.8 μ molZr, and Al/Zr=2000, ethene pressure 5atm are in 50 ℃ of reaction 30min.With the ethanolic soln termination reaction that contains 1% (weight ratio) hydrochloric acid, products therefrom is filtered, with washing with alcohol for several times, in 50 ℃ of vacuum-drying 24h.Catalytic activity is 393kgPE/molZr.atm.h.
Catalyzed ethylene polymerization carries out in the 0.1L autoclave under the anhydrous and oxygen-free condition, adds toluene 80ml successively in reaction system, contains the catalyzer of the high molecular of 11.47 μ molZr, and Al/Zr=600, ethene pressure 5atm are in 50 ℃ of reaction 30min.With the ethanolic soln termination reaction that contains 1% (weight ratio) hydrochloric acid, products therefrom is filtered, with washing with alcohol for several times, in 50 ℃ of vacuum-drying 24h.Catalytic activity is 121kgPE/molZr.atm.h.
Catalyzed ethylene polymerization carries out in the 0.1L autoclave under the anhydrous and oxygen-free condition, adds toluene 80ml successively in reaction system, contains the catalyzer of the high molecular of 5.8 μ molZr, and Al/Zr=600, ethene pressure 5atm are in 90 ℃ of reaction 30min.With the ethanolic soln termination reaction that contains 1% (weight ratio) hydrochloric acid, products therefrom is filtered, with washing with alcohol for several times, in 50 ℃ of vacuum-drying 24h.Catalytic activity is 285kgPE/molZr.atm.h.
Catalyzed ethylene polymerization carries out in the 0.1L autoclave under the anhydrous and oxygen-free condition, adds toluene 80ml successively in reaction system, contains the catalyzer of the high molecular of 5.3 μ molZr, and Al/Zr=600, ethene pressure 1atm are in 50 ℃ of reaction 30min.With the ethanolic soln termination reaction that contains 1% (weight ratio) hydrochloric acid, products therefrom is filtered, with washing with alcohol for several times, in 50 ℃ of vacuum-drying 24h.Catalytic activity is 99kgPE/molZr.atm.h.
Catalyzed ethylene polymerization carries out in the 0.1L autoclave under the anhydrous and oxygen-free condition, adds toluene 80ml successively in reaction system, contains the catalyzer of the high molecular of 5 μ molZr, and Al/Zr=600, ethene pressure 10atm are in 50 ℃ of reaction 30min.With the ethanolic soln termination reaction that contains 1% (weight ratio) hydrochloric acid, products therefrom is filtered, with washing with alcohol for several times, in 50 ℃ of vacuum-drying 24h.Catalytic activity is 111kgPE/molZr.atm.h.
Claims (1)
1. monodisperse porous organic polymer microsphere supported metallocene Preparation of catalysts method is characterized in that:
The composition of catalyzer: catalyzer is made up of A, B and C; Described A is polystyrene, Vinylstyrene and acrylonitrile copolymer for it; Be abbreviated as P (St-co-DVB-co-AN);
Described B is a metallocene, and its molecular formula is Cp
xMCl
y, in the formula, x=1 or 2, y=2 or 3, Cp are cyclopentadienyl group and derivative thereof, M is Ti or Zr;
Described C is a promotor, and it is methylaluminoxane, modified methylaluminoxane or three penta phenyl fluoride borons;
Preparation of catalysts:
1) preparation of monodisperse porous organic polymer microsphere
The preparation of a, linear polystyrene seed microballoon
Mechanical stirring is being housed, reflux condensing tube, nitrogen conduit, adding weight proportion in the four-hole reactor of temperature-detecting device is the vinylbenzene of 10:44:44:0.1:2, ethanol, ethylene glycol monoemethyl ether, Diisopropyl azodicarboxylate and polyvinylpyrrolidone PVP K-30 stir, stirring velocity is 60～120rpm, 60～80 ℃ of polymerization 12～24h of water-bath under the nitrogen protection, after reaction finishes, with reaction solution by centrifugal settling, remove supernatant liquid, to precipitate and use ethanol respectively, water washing, dry in vacuum drying oven, obtain the linear polystyrene seed microballoon of uniform particle diameter;
B, the seed swelling polymerization of two steps prepare monodisperse porous organic polymer microsphere supported A
(1) aqueous ethanolic solution of configuration 0.25wt% sodium laurylsulfonate obtains dispersion liquid;
Described ethanol water is solvent, and by the ethanol of mass ratio 5:1: water is formed;
(2) disperse polystyrene seed with dispersion liquid, wherein polystyrene seed: the mass ratio of dispersion liquid is 0.5:10～30, and ultra-sonic dispersion 5～20min obtains seed emulsion;
(3) disperse the 1-chlorododecane to help swelling agent with dispersion liquid, wherein the 1-chlorododecane helps swelling agent: the dispersion liquid mass ratio is 0.5:20～40, and ultra-sonic dispersion 10～60min obtains the bloated agent emulsion of hydrotropy;
(4) scattered seed emulsion and the scattered bloated agent emulsion of hydrotropy are mixed, place and mechanical stirring is housed, reflux condensing tube, nitrogen conduit is in the four-hole reactor of temperature-detecting device, in 25～35 ℃, swelling 8～24h under 80～120rpm carries out the first step swelling, obtains the activated seed emulsion;
(5) with dispersion liquid dispersing and mixing monomer, initiator, pore-creating agent; Wherein, mix monomer, initiator, pore-creating agent, dispersion liquid mass ratio are 10:0.1:10:30～60, and described mix monomer is made up of vinylbenzene, Vinylstyrene and other alkene, and each monomer proportion is not limit; Initiator is a dibenzoyl peroxide; Pore-creating agent is toluene, normal heptane or other inert solvents, and their ratio is not limit; Ultra-sonic dispersion 10～60min obtains mix monomer, initiator and pore-creating agent emulsion; Described other inert solvents comprise organic acid, alcohol, ester, aromatic solvent or have 12 carbon with interior any replacement aliphatic hydrocarbon;
(6) after the first step swelling finishes, scattered mix monomer, initiator and pore-creating agent emulsion are joined in the activated seed emulsion in (4) step, in 25～35 ℃, swelling 8～24h under 80～120rpm carries out the second step swelling, obtains the swollen microsphere emulsion;
(7) the configuration 5wt%PVPK-30 aqueous solution obtains stabiliser solution;
After (8) second step swellings finish; the swollen microsphere emulsion is transferred to standing demix in the separating funnel; remove the not remaining monomer of swollen; swollen microsphere emulsion after separating is transferred in the four-hole reactor; according to stabiliser solution: the mass ratio 2:1 of the swollen microsphere emulsion after the separation adds 5wt%PVP K-30 stabiliser solution; 60～80 ℃ of polymerization 12～24h of water-bath under the nitrogen protection; after reaction finishes with reaction solution centrifugal settling; remove supernatant liquid; to precipitate and use ethanol respectively; water washing; use the methylene dichloride extracting, vacuum-drying obtains monodisperse porous organic polymer microsphere supported A
2) preparation of monodisperse porous organic polymer microsphere supported metallocene
Under the anhydrous and oxygen-free condition,, carrier is carried out load according to a kind of in following three kinds of known typical supported catalyst agent methods with described monodisperse porous organic polymer microsphere supported A:
Direct and the carrier reaction of carrying method 1-metallocene catalyst:
Metallocene catalyst+monodisperse porous organic polymer microsphere supported A → monodisperse porous organic polymer microsphere supported A supported catalyst;
Carrying method 2-metallocene catalyst reacts with methylaluminoxane earlier, reacts with carrier then:
Metallocene catalyst+methylaluminoxane →+monodisperse porous organic polymer microsphere supported A → monodisperse porous organic polymer microsphere supported A supported catalyst;
Carrying method 3-monodisperse porous organic polymer microsphere supported A+ methylaluminoxane →+metallocene catalyst → monodisperse porous organic polymer microsphere supported A supported catalyst;
After any one above-mentioned mode of loading finishes, remove solvent, vacuum-drying obtains the monodisperse porous organic polymer microsphere supported metallocene Primary Catalysts; This metallocene Primary Catalysts and promotor C constitute the monodisperse porous organic polymer microsphere supported metallocene catalyzer.
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